Computational study of the dissociation of H–X acids (X=F, Cl, Br, I) in water clusters

2002 ◽  
Vol 117 (7) ◽  
pp. 3160-3168 ◽  
Author(s):  
Enrique M. Cabaleiro-Lago ◽  
Jose M. Hermida-Ramón ◽  
Jesús Rodrı́guez-Otero
Keyword(s):  
Water Clusters ◽  
Computational Study

Proton Acidity and Proton Mobility in ECR-40, a Silicoaluminophosphate That Violates Löwenstein’s Rule

2019 ◽  
Author(s):  
Michael Fischer
Keyword(s):  
Density Functional ◽  
Water Clusters ◽  
Computational Study ◽  
Acid Catalyst ◽  
Ab Initio Molecular Dynamics ◽  
Brønsted Acidity ◽  
Hydrothermal Route ◽  
Proton Mobility ◽  
Brönsted Acidity ◽  
A Minor

<p>The silicoaluminophosphate zeotype ECR-40, which has the MEI topology, contains linkages of AlO<sub>4</sub> tetrahedra via a common oxygen atom, thereby violating the famous “Löwenstein’s rule”. Due to the proven existence of Al-O-Al linkages in this material, it constitutes an ideal model system to study the acidity and mobility of protons associated with such unusual linkages. In addition, their properties can be directly compared to those of protons associated with more common Si-O-Al linkages, which are also present in ECR-40. In this work, static density functional theory (DFT) calculations including a dispersion correction were employed to study the preferred proton sites as well as the Brønsted acidity of the framework protons, followed by DFT-based ab-initio molecular dynamics (AIMD) to investigate the proton mobility in guest-free and hydrated ECR-40. Initially, two different proton arrangements were compared, one containing both H[O6] protons associated with Al-O-Al linkages and H[O10] protons at Si-O-Al linkages, the other one containing only H[O10] protons. The former model was found to be thermodynamically favoured, as a removal of protons from the Al-O-Al linkages causes a local accumulation of negative charge. Calculations of the deprotonation energy showed a moderately higher Brønsted acidity of the H[O10] protons, at variance with previous empirical explanations, which attributed the exceptional performance of ECR-40 as acid catalyst to the presence of Al‑O‑Al linkages. The AIMD simulations (<i>T</i> = 298 K) delivered no appreciable proton mobility for guest-free ECR-40 and for low levels of hydration (one H<sub>2</sub>O per framework proton). Under saturation conditions, framework deprotonation occurred, leading to the formation of protonated water clusters in the pores. Pronounced differences between the two types of framework protons were observed: While the H[O10] protons were always removed from the Si-O-Al linkages, the Al-O-Al linkages remained mostly protonated, but deprotonation did occur to a minor extent. The observation of a degree of framework deprotonation of Al-O-Al linkages differs from the findings reported in a recent computational study of hydrated aluminosilicate zeolites with such linkages (Heard et al., <i>Chem. Sci.</i> <b>2019</b>, <i>10</i>, 5705), pointing to an influence of the overall framework composition. Further inspection of the AIMD results showed that a coordination of water molecules to framework Al atoms occurred in many cases, especially in the vicinity of the Al-O-Al linkages, sometimes resulting in a pronounced modification of the linkages through additional bridging oxygen atoms. Given the changes in the local structure, it can be expected that such modified linkages are especially prone to break upon dehydration. Thus, in addition to elucidating the deprotonation behaviour of protons associated with different types of linkages, the calculations also provide insights into possible reasons for the instability of Al-O-Al linkages, clarifying why Löwenstein’s rule is mostly obeyed in materials that are formed via a hydrothermal route.</p>

Conformational structures of jet-cooled acetaminophen–water clusters: a gas phase spectroscopic and computational study

2017 ◽  
Vol 19 (6) ◽  
pp. 4840-4848 ◽  
Author(s):  
Ahreum Min ◽  
Ahreum Ahn ◽  
Cheol Joo Moon ◽  
Ji Hoon Lee ◽  
Yeon Guk Seong ◽  
...  
Keyword(s):  
Gas Phase ◽  
Water Clusters ◽  
Computational Study ◽  
Theoretical Calculations

Jet-cooled acetaminophen (AAP)–water clusters, AAP–(H2O)1, have been investigated by a combination of theoretical calculations and R2PI, UV–UV HB, IR-dip, IR–UV HB techniques in the gas phase.

scholarly journals Computational Study of Hydrogen Bond Interactions in Water Cluster-Organic Molecule Complexes

2021 ◽  
Author(s):  
Eduardo Romero-Montalvo ◽  
Gino A. DiLabio
Keyword(s):  
Hydrogen Bond ◽  
Organic Molecule ◽  
Organic Molecules ◽  
Water Clusters ◽  
Computational Study ◽  
Noncovalent Interactions ◽  
Structural Features ◽  
Binding Energies ◽  
Small Water ◽  
Hydrogen Bond Interactions

We present a computational study analyzing the noncovalent interactions occurring in complexes formed between small water clusters and selected organic molecules. We used DLPNO-CCSD(T)/CBS to calculate the binding energies (BEs) of these complexes. We subsequently analyzed the BEs in terms of the structural features of the found noncovalent interactions.

scholarly journals Computational Study of Hydrogen Bond Interactions in Water Cluster-Organic Molecule Complexes

2021 ◽  
Author(s):  
Eduardo Romero-Montalvo ◽  
Gino A. DiLabio
Keyword(s):  
Hydrogen Bond ◽  
Organic Molecule ◽  
Organic Molecules ◽  
Water Clusters ◽  
Computational Study ◽  
Noncovalent Interactions ◽  
Structural Features ◽  
Binding Energies ◽  
Small Water ◽  
Hydrogen Bond Interactions

We present a computational study analyzing the noncovalent interactions occurring in complexes formed between small water clusters and selected organic molecules. We used DLPNO-CCSD(T)/CBS to calculate the binding energies (BEs) of these complexes. We subsequently analyzed the BEs in terms of the structural features of the found noncovalent interactions.

Proton Acidity and Proton Mobility in ECR-40, a Silicoaluminophosphate That Violates Löwenstein’s Rule

2019 ◽  
Author(s):  
Michael Fischer
Keyword(s):  
Density Functional ◽  
Water Clusters ◽  
Computational Study ◽  
Acid Catalyst ◽  
Ab Initio Molecular Dynamics ◽  
Brønsted Acidity ◽  
Hydrothermal Route ◽  
Proton Mobility ◽  
Brönsted Acidity ◽  
A Minor

<p>The silicoaluminophosphate zeotype ECR-40, which has the MEI topology, contains linkages of AlO<sub>4</sub> tetrahedra via a common oxygen atom, thereby violating the famous “Löwenstein’s rule”. Due to the proven existence of Al-O-Al linkages in this material, it constitutes an ideal model system to study the acidity and mobility of protons associated with such unusual linkages. In addition, their properties can be directly compared to those of protons associated with more common Si-O-Al linkages, which are also present in ECR-40. In this work, static density functional theory (DFT) calculations including a dispersion correction were employed to study the preferred proton sites as well as the Brønsted acidity of the framework protons, followed by DFT-based ab-initio molecular dynamics (AIMD) to investigate the proton mobility in guest-free and hydrated ECR-40. Initially, two different proton arrangements were compared, one containing both H[O6] protons associated with Al-O-Al linkages and H[O10] protons at Si-O-Al linkages, the other one containing only H[O10] protons. The former model was found to be thermodynamically favoured, as a removal of protons from the Al-O-Al linkages causes a local accumulation of negative charge. Calculations of the deprotonation energy showed a moderately higher Brønsted acidity of the H[O10] protons, at variance with previous empirical explanations, which attributed the exceptional performance of ECR-40 as acid catalyst to the presence of Al‑O‑Al linkages. The AIMD simulations (<i>T</i> = 298 K) delivered no appreciable proton mobility for guest-free ECR-40 and for low levels of hydration (one H<sub>2</sub>O per framework proton). Under saturation conditions, framework deprotonation occurred, leading to the formation of protonated water clusters in the pores. Pronounced differences between the two types of framework protons were observed: While the H[O10] protons were always removed from the Si-O-Al linkages, the Al-O-Al linkages remained mostly protonated, but deprotonation did occur to a minor extent. The observation of a degree of framework deprotonation of Al-O-Al linkages differs from the findings reported in a recent computational study of hydrated aluminosilicate zeolites with such linkages (Heard et al., <i>Chem. Sci.</i> <b>2019</b>, <i>10</i>, 5705), pointing to an influence of the overall framework composition. Further inspection of the AIMD results showed that a coordination of water molecules to framework Al atoms occurred in many cases, especially in the vicinity of the Al-O-Al linkages, sometimes resulting in a pronounced modification of the linkages through additional bridging oxygen atoms. Given the changes in the local structure, it can be expected that such modified linkages are especially prone to break upon dehydration. Thus, in addition to elucidating the deprotonation behaviour of protons associated with different types of linkages, the calculations also provide insights into possible reasons for the instability of Al-O-Al linkages, clarifying why Löwenstein’s rule is mostly obeyed in materials that are formed via a hydrothermal route.</p>

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